1. Field of the Invention
The present invention relates to novel ethylenically unsaturated amine salts of sulfonic, phosphoric and carboxylic acids. More specifically, the invention relates to ethylenically unsaturated amine salts of alkylbenzene sulfonic acids, alkyl olefin sulfonic acids, alkyl alcohol sulfuric acid esters and alkoxylated alkyl alcohol sulfuric acid esters, and mixtures thereof. Additionally, the invention relates to ethylenically unsaturated amine salts of alkyl carboxylic acids and alkyl phosphoric acids. The salts are polymerizable, surface active agents which are useful in a variety of applications, especially in detergent formulations and in emulsion polymerization processes.
2. Description of the Related Art
Detergents, shampoos, cleansers, soaps, and the like, are used to perform a wide variety of household and industrial cleaning operations and are formulated to give compositions which produce optimum performance under the contemplated end use conditions. Typically, these compositions contain a variety of surface active agents known to the art, in the form of anionic, nonionic, amphoteric, and/or cationic surfactants. The anionic surfactants used in the compositions are typically in the form of alkali metal (lithium, sodium, potassium), alkaline earth (calcium, magnesium), ammonium and/or alkanolamine salts of the corresponding anionic acid. In formulating such compositions, it is desirable to have a variety of surface active agents available for producing and optimizing the compositions.
Surface active agents also find use in applications beyond typical detergent or shampoo formulations. For example, in a conventional emulsion polymerization of ethylenically unsaturated monomers, one or more surfactants are used to emulsify the monomers and the resulting polymer products, i.e., latexes. The monomers used in emulsion polymerization reactions are generally water-insoluble, but may also be water-soluble. During the polymerization, small portions of monomer are suspended in a continuous aqueous phase. Typically, a water soluble surfactant is present within the aqueous phase to aid in the suspension of the monomer, with subsequent polymerization via a free-radical polymerization. The water soluble surface active agents, i.e., surfactants, utilized in emulsion polymerization reactions are typically anionic, nonionic, cationic, or zwitterionic surfactants or mixtures thereof.
In a traditional emulsion polymerization reaction, discrete, solid polymeric particles are formed during the course of the reaction to form a polymer product latex. Typically, the surfactant employed in such a traditional emulsion polymerization reaction does not react with, i.e., become chemically bonded via carbon-carbon bond formation, the discrete polymeric particles. Rather, the surfactant remains unreacted in the polymer product latex after the emulsion polymerization reaction is complete. The unreacted surfactant can interfere with the performance of such polymerization products in coating, adhesive, sealant and elastomer (CASE) applications, non-woven fiber applications and carpet backings. The unreacted surfactant may cause pealing of a latex paint coating, and decreased moisture resistance and scrubability resistance in various CASE applications. Additionally, residual surfactant can cause an undesirable xe2x80x9cbloomingxe2x80x9d that leads to surface irregularities in a resulting CASE that is applied to a substrate.
Several proposals have been made in the prior art to employ a polymerizable surfactant as the surface active agent during an emulsion polymerization reaction. U.S. Pat. No. 5,478,883 (incorporated herein by reference) describes the use of ethylenically unsaturated polymerizable water-soluble nonionic surfactants formed by the reaction of a diallylamine compound with ethylene oxide, propylene oxide or butylene oxide, in emulsion polymerization reactions. Similarly, U.S. Pat. No. 5,162,475 (incorporated herein by reference) provides alpha-beta ethylenically unsaturated poly(alkylenoxy) polymerizable surface active compounds for use in emulsion polymerization. For additional examples of polymerizable surfactants for use in emulsion polymerization processes, see U.S. Pat. Nos. 4,377,185 and 4,049,608.
The present invention provides ethylenically unsaturated amine salts of sulfonic, phosphoric or carboxylic acids, or mixtures thereof. The amine salts of the present invention are polymerizable, surface active agents suitable for use as primary or secondary surfactants, and/or as surfactants in emulsion polymerization reactions.
Accordingly, the present invention provides novel ethylenically unsaturated amine salts of sulfonic, phosphoric or carboxylic acids, or mixtures thereof, which are polymerizable, surface active agents in a variety of applications. It has been discovered that these surface active agents are useful, for example, in detergents (e.g., laundry detergents, dish detergents, automatic dishwasher detergents, etc.), shampoos, 2-in-1 shampoos, 3-in-1 shampoos, cleansers, soaps, liquid hand soaps, body washes, agricultural herbicide and pesticide formulations and the like. Additionally, the surface active agents of the present invention are especially useful in emulsion polymerization reactions and are generally capable of polymerizing with themselves and/or co-polymerizing with other ethylenically unsaturated monomers of the type which are commonly employed in emulsion polymerization reactions.
The surface active agents of the present invention are prepared from readily available, economical raw materials, and generally, their preparation does not require any special handling or equipment. The polymerizable surface active agents may be prepared in a batch mode or a continuous mode; they may be prepared by contacting the ethylenically unsaturated amine with the acid or contacting the acid with the ethylenically unsaturated amine. By contacting it is meant that the acid(s) is added to the ethylenically unsaturated amine(s) and the components are mixed, or the ethylenically unsaturated amine(s) is added to the acid(s) and the components are mixed. Typically, the acid is present as an anion and the base is present as a cation (i.e. a quaternary nitrogen) in the mixture. The acid and nitrogenous base form salts or quaternary nitrogen compounds. As known by one skilled in the art, upon mixing the acid and nitrogenous base together, the nitrogenous base becomes a conjugate acid and the acid becomes a conjugate base.
The surface active agents and blends of surface active agents may be prepared in a variety of forms, including but not limited to, liquids, solutions, solids, powders, flakes, semi-solids, gels, xe2x80x9cringingxe2x80x9d gels, G-phase liquids, hexagonal phase solids, or thick pastes. The surface active agents may be spray dried, flaked, extruded, and the like. Although not critical to the present invention, the polymerizable, surface active agents may be prepared xe2x80x9cneatxe2x80x9d or in a conventional solvent such as water, low molecular weight alcohol or hydrocarbon, or a mixture thereof, to produce an aqueous solution of the surface active agent The present invention encompasses surface active agents as salts in dry form and as aqueous solutions. Salts of the surface active agents may be isolated by drying a solution of the surface active agents; a solution of surface active agents may be prepared by dissolving the salt of the surface active agent in water, low molecular weight alcohol or hydrocarbon, or a mixture thereof.
Individual surface active agents of the present invention may be prepared and mixed together to produce a surface active mixture comprising xe2x80x9cneatxe2x80x9d surface active agents or an aqueous surfactant blend. Additionally, neat or aqueous blends of the surface active agents may be prepared by contacting a blend of two or more ethylenically unsaturated amines with one acid, or by contacting a blend of two or more ethylenically unsaturated amines with a blend of 2 or more acids. Conversely, blends of the surface active agents may be prepared by contacting a blend of two or more acids with one ethylenically unsaturated amine, or by contacting a blend of two or more acids with a blend of two or more ethylenically unsaturated amines.
These and other advantages of the present invention will be apparent from the following description of the invention.